Ring-substituted n-allyl-2-oxazolidinone compounds and polymers thereof



William F.

Mich, assignors to The Dow Chemical Company, Midsass ash RING sunsm'nmn,N -ALLYL 2 oXAzoLrnr- NONE coMPoUNns AND PGLYMERS 'rrmnnor Tousignantand Wilhelm E. Walles, hiidland,

land, Mich, a corporation of Delaware No Drawing. Filed May 19, 1958,Ser. No. 735,956 7 Claims. (Cl. 26077.5)

The present invention is germane to the organic chemical arts. It hasmore pertinent reference to certain ringsubstitutedN-allyl-Z-oxazolidinone compounds, including compounds having alkyl andaryl ring substituent-s, which are new and useful monoethylenicallyunsaturatedmonomeric substances, and to various derivatives thereof parrticularly polymeric and resinous products that have great utility andprovide for many benefits and advantages in xnumerous applications.

wherein each X is independently selected from the group consisting ofhydrogen, allryl radicals containing from 1 r to about 4 carbon atomsradicals),

(particularly methyl and ethyl in m has a numerical value of at least 1.

A particular object is to provide monomeric ring-sub,- stitutedN-allyl-Z-oxazolidinone compounds of the indicated varieties that arecharacterizable vin having the generic structure:

wherein each X is as above defined.

A specific object is to provide monomeric N-a1lyl-5-methyl-2-oxazoli-dinone, which is of the general structure according toFormula II, wherein the X in the -position of the ring is methyl and Xin the 4-position is hydrogen.

A further object, and one that is of considerable magnitude, is toprovide polymeric products, including homopolymers and variouscopolymers of high polymer nature, that are derived from the N-allyl-2-oxazolidinone monomers of the indicated varieties, especially thosederived from N-allyl-5-methyl-2-oxazolidinone.

According to" the present invention, the new monomeric compounds whichpossibilitate the achievement of the above indicated and cognate objects(including the formation of new polymeric products) are of the generalstructure of Formula 11. In general, the monomeric ringsubstitutedN-allyl-2-oxazolidinone compounds of the present invention areordinarily clear, colorless or water- White liquids at, or at leastnear, normal room temperatures. Some of the monomers, however,particularly the aryl (such as phenyl) ring-substituted derivatives, arenormally solid, meltable substances. The monomers are ordinarily solublein water and lower aliphatic alcohols, such as methanol, ethanol,propanol and many other organic solvents. This is generally true forN-allyl-S-methyl- Z- oxazolidinone and the other lower alkyl (such asethyl) ring-substituted species. Bulky substituent units (such as 1phenyl) often tend to diminish the watersolubility of the monomericring-substituted N-allyl-2-oxazolidinone coinpounds. V I

For example, N-allyl-S-methyl-Z-oxazolidinohe is a clear,actuallywater-white liquidat room temperature which is Water-soluble aswell as being soluble in metha n01, ethanol, styrene, 'diethyleneglycol, diethyl ether, 2- pyrrolidinone (sometimes called 2-pyrrolidone)chloroform, dimethylformamid, nitrome-thane, acetic acid, anilineethylene carbonate, the dimethylethers of di-, tri-, or tetra-ethyleneglycol, dimethyl sulfoxide, and the like.N-allyl-5-methyl-2-oxazolidinone is insoluble in such solvents ascyclohexanol, hexane, kerosene and mineral oil. Under an absolutepressure of about 0.4 mm. Hg, pure N-allyl-5-methyl-2-oxazolidinoneboils at a temperature of about'80 C. Of course, the degree of impurityof the monomer may tend to alter the boiling'point of the material tosome extent. Monomeric N-allyl-S-methyl-Z- oxazolid-inone has arefractive index, taken at C., of about 1.4631 and a specific gravity,takenat 25 C. and

' referred to water at 4 C., of about-l.0633. Upon infraand arylradicals containing from 6 to about- 10 carbon atoms (particularlyphenyl, alkyl substituted. phenyl, etc.), with the limitation that notmore than one,

of said substituent members can be hydrogen, and wheresuch. as a sodiumor red analysis, the monomeric compounds exhibit the characteristicabsorption bands that are obtained when N-allyl groups and orally, theunstabilized monomers become discolored to a very light shade of yellowwithin several days of continued exposure to light. However, the dark,particularly when they are maintained under an atmosphere of nitrogen,their natural stability is'good. Thus, the monomeric ring-substitutedN-allyl-Z-oxazolidinone compounds may be stored safely for prolongedperiods. when maintained so .as to be protected in the indi-- catedmanner. The monomeric compounds react with solutions of bromine inchloroform, as evidenced by rapid discoloration of the halogen solution,due to the bromination of the allyl groups-in the monomer. Dilutesolutions of potassium permanganate and the like reagents rapidlyoxidize the allyl group allyl-2-oxazolidinone compounds: 1

The monomeric ring-substituted'N-allyl-Z-Oxazolidinone compounds of theFormula II'may advantageously be prepared by the reaction between analkali'm'etal salt,

substituted 2-oxazolidinone compound and allyl bromide at a moderatelyelevated temperature. For purposes of illustration, the'preparation ofone of the monomers; of the present invention (N-allyl-Smethyl-2-oxazolidinone) is representedby the following equation:

It is desirable for the reaction. to be conducted in a when theyarekeptin:

of monomeric ring-substituted N- potassium salt, of the starting ring- 37 Suitable solvent vehicle, such as benzene and the like solve tsofi he.benzene series. formed with benefit at temperatures from about 25 to 80?7C It will occur under any desired pressure although it isgciierallyheneficial, to, use. atmospheric, pressure for the reaction.Ordinarily, good conversions, andyields of desired product from theconverted starting material= can, be'realized within reaction periods of24, hours or less.,' By way of illustration, conversions and, yields in:the; neighborhood of 8Q-90 percentand higher:- are easily,

The reaction may. be per-i a possible to attain, The'desired monomericring substiri V t e -ally r g-qxaz i noa Products an be r cov r d sasliI-cm he r act n ma sus g pr c d r hat-will be ea i p r nt. ho e that r kle n, the a This ss y ex rac r ct na i llation, Pr cipi: tation and/orstripping techniques, can be employed for product. isolation, depending,upon the regpirements. and eircumst ces ofi, speciiic situations,

a b11111; P l meriza on) as el -pahme a don,

being polymerized is orare not at; all soluble; or only than s' sbls-L tina v nefic al a e. p y-1 merigation to he conducted at a, temperature,between, about 50 and 100 C., although this may vary with the,

particular catalyst, monomer and solvent or carrier, if any, used andthe type of reaction being conducted. Suitable catalysts or initiatorsfor polymerization of the monomeric ring-substitutedN-allyl-Z-oxazolidinone compounds include the peroxygen catalysts, suchashydrogen peroxide, lauroyl peroxide, benzoyl peroxide, potassiumpersulfate.or;the.like, and-ionic catalysts such as borontrifluorideI-ether. complex, as well: as irradiation under theinfluence. ofshigh energyfelds, such as X rayandgamma. radiations fromradioactive materials. (i.e.,

cohalt 6 l), cesium-137, etc.)- and. high energy electron heamsgeneratedfrom linear, accelerators, resonant-transformers, electrostaticgeneratorsrandthe like. Such diverseiorms of radiatiomcatalysts astheactinic radiations,

-allyl- 2i oxaz olidinone,monomers dergo polymerization inmass; (whichis oftentimes;

s, lb si t llv sy v l fiq ssntr fipa n; a ueous: th x vlt qsa n; mi l-19a O he disn t io ia i sh w is e Parti ular-msnsmen rmqn me mayadvantageously be prepared as high polymers having a number averagemolecular weight, for example, in the range irom 10 to 50 thousand andhigher (as determinable from Fikentscher K-values of about 5-10 ormore), and a structural arrangement containing recurringpolymerizedunits that may be depicted in the following way.

Kira- 0 V ,l X111 1 6:0

, \H 2/ (111) wherein, the X substituents are as, above defined andlimited and n is. a plural integer, preferably one whose numericalvalueis greater than 5 or 10,.to, 50, or so and which may be as largeas, 1900-2300 or'more Thev hydrogen'(or other terminal units) whichoccur. inhomo: polymeric and other polymeric, compositions are, not

I shown in Formula HI since such details, are readily, un-

dsI ItQQ y. he i an Q mur e, ower an ,.h sl

7 molecular weight polymers can also, be prepared, It

should be taken into account in connection. with the above, mentionednumber average molecular weight ranges that the indicated numericalvalues depend upon the peculiarities of the method of expression whichis employed for such statistic; Much higher values, espe-' cially in thehigher ranges, are equally accurate when the molecular weight isotherwise expressed. Thus, ac cording to the commonly used concept of,weight .aver' age" molecular-weight (as defi nedby Frank and Levy,

includingultrayiolet light, may alsorbeutilizedr The azo" y typecatalysts, such as a,uf-azobisisohutwonitrilel are not:

suitable initiators for theipolymerizationa reaction,

Copolymers ofvarious1 monomeric ring substituted:

N- allyhz -oxa zolidone :compoundsof the lEOI'IfiUlflrH', particularlythos containing} i alhyh'substituents, with one another and other mQQmeric substances copolymeriz-t. able-therewith may he preparedrin ways;analogous to those, described; in, the; foregoing, includingsuspension.-

and emulsion polymerization techniques, To suchends,

yllto uene, acrylonitrile, vinyl chloride, vinylfluoride,

meric .-acrylate and methacrylate compoundasvinyl ace: te vinyl 1 p q qat nd e like ethenoids, (g y ar b e in; ontain g sC 2= sr p ichidin'gjltheg N-vinyl l lactams, such as ,Nrvinyl l-pyrrolidinone,""the several; N.-.vinyl2,-oxazolidinones;, such v asN-vinyl-Z-oxazolidihone, NWinyl-S-rnethyl 2, oxazolidinone, etc.,N-vinyl-3-morpholinone and so forth; Be-

sides those mentioned-in the foregoing, other monomers that may beemployed suitably for the preparation of copolymerized ring substitutedN-allyl-Z-oxazolidinone include those that have been disclosed anddelineated in ,United States Letters Patent No. 2,818,362. 7

When copolymers are prepared, it is frequently desirable fortthemonomeric ring substituted N-allyl-Z-oxazolidinone compound'that isemployed (or for a mixture of, such monomers of the Formula II) toconstitute at least about 10 percent by weight of the mixture ofcopoly-I merizabletmaterials, e.g., fro' n 10 to 90 or 95 or even as highas99percent byf weight of such a mixture.

i 1 .Therins suhs itutedgN-allylrz-o a qlid ncnspoly ers 7 i done,chloride,v rnethyl acrylateQ ethylr acrylate;f' .rnethyl -methacrylate,ethylmethacrylate and other monoer ,monoethylenicallyunsaturatedmonomers suchas styrene, I

Journal of Polymer Science,l0, 371-8' (1953 T), the mo lecular weight orthepolymers, especially in the. higher ranges, are significantly larger,In any event,- the indi cated molecular weight values, as; well as thevalue of n are intended to be mere ap roximate averages ratherthan'discrete limits.

Generally, thering substituted poly-N allyl-2-oxazolidinones arehygroscopic, water-soluble materials.

They can usually be. obtained as-light to white colored,

The ring substituted poly N-allyl-2-oxazolidinones,- can;

generally.-,bemolded under pressureat temperaturesibe;

' tween aboutlQO and ZQO? C. to-produceclear, hardiand brittle or. s i atur s many of h ch rewaten soluble.

Because of their excellent aflinity for, many a wide variety 'ofdyestufts (including ,direct; basic, acid, vat and:

other classes of dyes), the ring substituted polyeN allylLoxazolidinones ,can, ordinarily. be employed. with; great benefit asdyeassisting adjuvantsf or. dye-receptorsl iorr synthetic textilefibersand other shaped articles, oiinorf mally. difliculotqdye;synthetic, polymers.

connection with fiber-forming; compositions and; filae mentary shapedarticles produced therefrom of the.- vari-- ousacrylonitrile polymers,particularly polyacrylonitrile.v Besidessuchdesirable utility, certainofthe ringsubsti- I tuted; poly-N-allyle2-oxazolidinones, exhibitadditional utilitiesof un usual attractiveness For example, poly-N allyl-imethyhZ-oxaaolidiuone= 'andcertain other of'the ringsubstitut'edpoly-N-allyl:2:0xazolidinones oftheFormulajIII ,may he, employed withadvantage: in wave or curlsetting formulations,or'compositionsfor humanhair; as dye-stripping, agentsv for textile goods and as other Inthis-.ca-s. pacity, they may be utilized with exceptionalbenefit-invarieties of textile assistants; for beverage clarificationpurposes and in numerous other applications.

The invention is further illustrated in and by the following exampleswherein, unless otherwise indicated, all parts and percentages are to'betaken by weight.

EXAMPLE A Preparation of N-Allyl- Methyl-2-0ruzolidinoize To a one literresin kettle, equipped with a water condenser, stirrer, dropping funneland thermometer, there was added about 117.0 grams (0.9 mole) of3-sodio-5 methyl-Z-oxazolidinone and 1.2 liters of dry benzene. Thecharge was agitated and to thestirring salt suspension there was added,via stillicide, about 115.0 grams (0.9 mole) of allyl bromide at atemperature of 52 C. over a period of three hours. When the addition wascomplete, the temperature of the reactionmass was gradually: raisedtoreflux (78.582 C.) and held at this temperature vfor'a period of 16hours. Over this period of time the sodium. bromide that was formedprecipitated out of the reaction mass. At the termination of thisperiod, the reaction mixture was cooled and the sodium bromide filtereded. The amount of sodium bromide obtained was about 87 grams, 0.85 mole)indicating a 95 percent conversion.

Benzene was removed from the reaction mass under reduced pressure ofabout mm. Hg absolute at ,a temperature of 50 C. When the benzeneremoval was essentially complete, an equal volume of water was added tothe remaining liquid giving a homogenous solution. The solution was thenextracted three times with equal portions of diethyl ether. Theextracted portions were then subjected to mild vacuum mm. Hg absolute)to remove the ether and the remaining oleaginous residue was then vacuumdistilled. About 115.8 grams of monomericN-allyl-5-methyl-2-oxazolidinone was collected as .the fraction at 80C./ 0.4 mm. Hg. This represented an 82.5 percent yield of desiredmonomer.

The monomer was a water-white liquid that was soluble in water, loweralkyl alcohols and diethyl'ether. Its properties were as follows:

B.P. so" c./0.4 mm. Hg. N 1.4'631. D 1.0633. Empirical formula C H O N.

Analysis Percent C PeroentH PercentN Found 0.13 7.92 9.13 Calculated59.56 7.80 i 9.93

Similar results are obtained when the foregoing is repeated excepting touse alkali metal salts of 5-ethy1-2- oxazolidinone;4,5-dimethyl-Z-oxazolidinone; 5phenyl-2- oxazolidinone; and the like toprepare corresponding ringsubstituted N-allyl-2-oxazolidinone monomersand when other starting materials are used to make monomers within thescope of Formula II.

EXAMPLE B Preparation of Poly-N-A llyl-5-Methyl-2-Oxaz0lidin0ne Into alarge test tube there was placed about 20.0 grams of the monomerprepared in the first example. To this this there was added about 0.5gram of ditertiary 'butyl peroxide as a catalyst. Nitrogen was spargedinto 6 cedure gave a very light buff-colored powder when vacuum dried. I

The polymeric N-allyl-S-methyl-2-oxazolidinone was found to be solublein acetone, alcohols, and methylene chloride; .very slightly soluble inbenzene; and insoluble in diethyl ether and Skelly solvent 100-140 C.

The polymeric product was found to have a Fikentscher 'K-value of about12.1 and an average approximate molecular weight of about 13,000.

Its melting point, using the Fisher Johns Apparatus, was92 C. for fusingand 115 'C. for melting to a yellow liquid. Its density was about 1.28grams per cubic centimeter. The polymericproduct molded at 100 .C. under5,000 p.s.i. plate pressure to a clear, light. yellow, brittle Similarresults are obtained when the foregoing is re peated in order toprep-are such polymers as poly-N-allyl- 5-ethy1-2-oxazolidinone;poly-N-allyl-4,5-dimethyl-2-oxazolidinone; poly-N-a1lyl-4-methyl-2oxazolidinone; poly- N-allyl-4-ethyl-2-oxazolidinone;poly-N-allyl-S-phenyl-Z- oxazolidinone; and other'of the homopolymers ofFor- .EXAMPLE c g Use of Poly-N-Allyl-5-Methyl-2-Oxazolidinong (PAOM) Apolyacrylonitrile fiber is obtained in a water-hydrated mula III, usingappropriate starting monomers for their preparation.

or aquag el condition in which it contains about'2 parts of water toeach part of polymer therein. The aquagel, which is oriented by wetstretching after extrusion, is obtained in a known manner bysalt-spinning a solution containing about 10 percent of fiber-formingpolyacrylonitrile ina percent aqueous zinc chloride solvent thereforinto an aqueous coagulating bath containing about 42 percent of zincchloride. The aquagel fiber is immersed at room temperature in a 3percent aqueous solution of poly-N-allyl-S-methyl-Z-oxazolidinone havinga Fikentscher K-value of about 12 until about 10 percent (on the dryweightv of the resulting fiber product) of the watersoluble polymer isincorporated therein. After the impregnation, the fiber product is driedat about 150 C. for 30 minutes to convert it to a hydrophobic form. Itis found to be readily dyeable to deep and level shades of colorationupon a 4 percent dyeing in the conventional manner with Calcodur Pink2BL, a direct dyestutf having the Colour Index 353. The PAOM-containingfiber product is also readily and excellently dyeable with suchdyestuifs as Sevron Brilliant Red 46 (formerly known as Basic Red4GColour Index Basic Red 14), a basic dyestuff; Amacel Scarlet BS, anacetate dyestuif (American Prototype No. 244); Calcocid AlizarineViolet, an acid dye (Colour Index 1080) and the like. a 7

Excellent results similar to those demonstrated'in the stitutedN-allyl-2-oxazolidinone polymers of the Formula III and copolymerscontaining such recurring units,

and when the polymeric products are utilized for such purposes asdye-stripping agents, for clarifying such beverages as beer and wine, inhair setting formulations, and in numerous other applications.

What is claimed is: 1. A monomeric compound of the structure:

KEG-'5) XHC\ =0 N Ha-CH=CH2 (II) wherein each X is independentlyselected from the group consisting of hydrogen, alkyl radicalscontaining from 1 to 4 carbon atoms, and aryl radicals containing from 6to 10carbon atoms, with the limitation that not more than 1 of said Xsubstituents can be hydrogen.

2. Monomeric N-allyl-5-methyl-2-oxazolidinone. 3. An addition polymerhaving as an essential constituent. of its.- polymeric structurematerial interpolymerized characterizing proportions of the recurringgroug:

' wherein each independently selected horn the, group.

consisting of hydrogen, alkylradicals containing from. 1

to '4 carbon atoms and 'aryl radicals containing from 6 to" 10 carbonatoms, with the'limitationftliat not more than 1: of SaidJXisubstituentScan be hydrogen. 7

4. An addition copjolymer polymerized'from ingredients including; (101amonomer and (b)fa,compound" which is: different from" the compoundiofr(2: )1, is copol'ymerizatile therewith and' which contains ayCH -C',grouping.

5; The 'copolymer in claim 4, wherein the compound, of (b) is a vinylcompound.

6. An addition polymer of N-alIyl-S-methyl-2-oxazolidinon'erFL a.

v 7csA homopolymer characterizedmy having as.chemia callycombinedrecurrent groups in itsimoleculez' wherein each Xi is independentlyselected from thegroup consisting of hydrogen, ,alkyl radicalscontaining from 1 to 4 carbon atonis,rand aryl radicals containing from6: to 10-c arbonatoms; with the limitationrthat not more than one ofsaid X substituents can be hydrogen.

References Cited in thefii'e'of'this' patent ,7 UNITED STATES PATENTS.

OTHER REFERENCES 1 Ham: Textile '"Research' Iouri, T, 1954, pp; 597,664-6142" Great Britain Jam 26,. 1955'.

1. A MONOMERIC COMPOUND OF THE STRUCTURE: